Boron-nitrogen compounds and their use

Abstract

This application relates to the field of display technology, and more particularly to a boron nitride compound and its applications. The boron nitride compound provided in this application can produce deep blue light emission, and its binuclear structure has carbon, nitrogen, and oxygen atoms arranged alternately on the same plane, which helps to improve exciton utilization and increase luminous brightness.

Description

Technical Field

[0001] This application relates to the field of display technology, and more particularly to a boron nitride compound and its applications. Background Technology

[0002] After nearly 30 years of development, organic light-emitting diodes (OLEDs) have entered the commercial application stage in the field of small and medium-sized displays. Among them, red and green light materials and technologies have reached the standards for commercial application, but blue light still faces the problems of low brightness and short device life.

[0003] Currently, blue light has low brightness and short lifespan. This is mainly because traditional fluorescent materials can only utilize singlet excitons (25%), making it difficult to achieve higher external quantum efficiency (EQE). Therefore, how to effectively improve the exciton utilization rate of the EML layer in OLED devices has become an urgent problem to be solved. Summary of the Invention

[0004] Based on this, embodiments of this application provide a boron nitrogen compound and its application.

[0005] To address the aforementioned technical problems, this application provides a boron-nitrogen compound, employing the technical solution described below:

[0006] A boron-nitrogen compound with the general structural formula shown in formula (I):

[0007]

[0008] Each time X appears, it is independently selected from either carbon or nitrogen;

[0009] A includes sulfonyl groups, C6-C6 groups. 60 At least one of the azirroyl groups;

[0010] R1 to R4 are each independently selected from hydrogen, deuterium, amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, and substituted or unsubstituted C1 to C4 groups. 30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkyl mercapto, substituted or unsubstituted C1-C 30 Alkylamine, substituted or unsubstituted C1-C 30 Alkyl carbonyl, substituted or unsubstituted C1-C 30One or more of the following: alkoxycarbonyl, aryl with 6 to 60 substituted or unsubstituted ring atoms, heteroaryl with 5 to 60 substituted or unsubstituted ring atoms, arylamino with 6 to 60 substituted or unsubstituted ring atoms, aryloxy with 6 to 60 substituted or unsubstituted ring atoms, arylthiol with 6 to 60 substituted or unsubstituted ring atoms, heteroarylamino with 5 to 60 substituted or unsubstituted ring atoms, heteroaryloxy with 6 to 60 substituted or unsubstituted ring atoms, and heteroarylthiol with 6 to 60 substituted or unsubstituted ring atoms;

[0011] When substituted, each substituent is independently selected from hydrogen, deuterium, halogen, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C2. 30 One or more combinations of alkyl, aryl with 6 to 30 ring atoms, and heteroaryl with 5 to 30 ring atoms.

[0012] This application also provides a composite material comprising organic functional materials and the aforementioned boron-nitrogen compounds.

[0013] This application also provides the application of the above-mentioned boron nitrogen compounds in ink preparation.

[0014] This application also provides a light-emitting device, which includes a first electrode, a light-emitting layer, and a second electrode stacked together; wherein the material of the light-emitting layer includes the aforementioned boron nitride compound, or the material of the light-emitting layer includes the aforementioned composite material.

[0015] This application also provides a display device, which includes the boron nitride compound as described above, or the composite material as described above, or the light-emitting device as described above.

[0016] Compared with the prior art, the embodiments of this application have the following main advantages:

[0017] The boron-nitrogen compound provided in this application can produce deep blue light emission. In its binuclear structure, carbon, nitrogen, and oxygen atoms are arranged alternately on the same plane, which helps to improve exciton utilization and increase luminescence brightness. Attached Figure Description

[0018] To more clearly illustrate the solutions in this application, the accompanying drawings used in the description of the embodiments of this application will be briefly introduced below. Obviously, the accompanying drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the structure of the light-emitting device in an embodiment of this application. Detailed Implementation

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein in the specification of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having," and any variations thereof, in the specification, claims, and foregoing drawings of this application, are intended to cover non-exclusive inclusion. The terms "first," "second," etc., in the specification, claims, or foregoing drawings of this application are used to distinguish different objects, not to describe a particular order.

[0021] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0022] This application provides a boron-nitrogen compound with the general structural formula shown in formula (I):

[0023]

[0024] Each time X appears, it is independently selected from either carbon or nitrogen;

[0025] A represents an electron-withdrawing bridging group, including sulfonyl groups and C6-C6 groups. 60 At least one of the azirroyl groups;

[0026] R1 to R4 are each independently selected from hydrogen, deuterium, amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, and substituted or unsubstituted C1 to C4 groups. 30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkyl mercapto, substituted or unsubstituted C1-C 30 Alkylamine, substituted or unsubstituted C1-C 30 Alkyl carbonyl, substituted or unsubstituted C1-C 30One or more of the following: alkoxycarbonyl, aryl with 6 to 60 substituted or unsubstituted ring atoms, heteroaryl with 5 to 60 substituted or unsubstituted ring atoms, arylamino with 6 to 60 substituted or unsubstituted ring atoms, aryloxy with 6 to 60 substituted or unsubstituted ring atoms, arylthiol with 6 to 60 substituted or unsubstituted ring atoms, heteroarylamino with 5 to 60 substituted or unsubstituted ring atoms, heteroaryloxy with 6 to 60 substituted or unsubstituted ring atoms, and heteroarylthiol with 6 to 60 substituted or unsubstituted ring atoms;

[0027] When substituted, each substituent is independently selected from hydrogen, deuterium, halogen, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C2. 30 One or more combinations of alkyl, aryl with 6 to 30 ring atoms, and heteroaryl with 5 to 30 ring atoms.

[0028] The boron-nitrogen compound provided in this application has a BN-type binuclear structure in which carbon, nitrogen, and oxygen atoms are alternately arranged in the same plane. This helps to narrow the spectrum, reduce the ΔEST (single-triplet energy gap), and thus increase the RISC (reverse intersystem crossing) rate. It avoids concentration quenching or TTA caused by the inability of triplet excitons to upconvert to singlet states. The binuclear emission further enhances PLQY (photoluminescence quantum yield), thereby further improving device efficiency, exciton utilization, and luminescence brightness. Introducing electron-withdrawing bridging groups between the two nuclei can increase the band gap and form deep blue emission. In other words, the boron-nitrogen compound can be used as a BN-type binuclear deep blue luminescent material for the luminescent layer of organic light-emitting devices.

[0029] In one embodiment, R1 to R4 are each independently selected from one of hydrogen, deuterium, halogen atom, cyano, C1 to C5 alkyl, C1 to C5 alkoxy, C1 to C5 alkyl mercapto, and C1 to C5 alkyl amine.

[0030] In one embodiment, A includes a sulfonyl group and C6-C6 groups. 60 At least one of the azaaryl groups. The sulfonyl group has the following structure:

[0031]

[0032] In this structure, * represents a connection site.

[0033] In one embodiment, A is selected from one or more of the following structural formulas:

[0034]

[0035] Each time Y appears, it is independently selected from carbon or nitrogen, and at least one Y in each structure is selected from nitrogen;

[0036] n1 to n5 are integers from 1 to 8;

[0037] Each of R5 to R9 is independently selected from one or more combinations of hydrogen, deuterium, halogen atom, cyano, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkyl mercapto, C1-C5 alkylamino, substituted or unsubstituted aryl group having 6 to 10 ring atoms; when substituted, each of the substituents is independently selected from one or more combinations of hydrogen, deuterium, halogen, amino, hydroxyl, carboxyl, nitro, sulfonic acid group, mercapto, cyano, C1-C5 alkyl, aryl group having 6 to 10 ring atoms, heteroaryl group having 5 to 10 ring atoms.

[0038] In one embodiment, A is selected from one of the structures shown in equations (1-1) to (1-24):

[0039]

[0040]

[0041] In equations (1-1) to (1-24), * represents the connection site.

[0042] In one embodiment, the boron nitrogen compound represented by Formula I includes, but is not limited to, the compounds represented by M1 to M42 below:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] The application also provides a composite material comprising an organic functional material and one or more of the boron-nitrogen compounds described in the above embodiments.

[0054] In one embodiment, the mass ratio of the organic functional material to the boron nitride compound ranges from (80:20) to (99:1), preferably from (95:5) to (99:1). In this embodiment, the doping amount of the boron nitride compound is 1% to 20%. Within this range, it helps to narrow the spectrum, reduce the ΔEST (singlelet-triplelet energy gap), and thus improve the RISC (Reverse Intersystem Crossing) rate. This avoids concentration quenching or TTA due to the inability of triplet excitons to upconvert to singlet states. Simultaneously, the dual-core emission further enhances the PLQY (Photoluminescence Quantum Yield), thereby further improving device efficiency.

[0055] Optionally, the mass ratio of the organic functional material to the boron-nitrogen compound is within any one or any two of (80:20), (82:18), (85:15), (88:12), (90:10), (92:8), (95:5), (97:3), and (99:1).

[0056] In one embodiment, the organic functional material includes at least one of BH1, BH2, CBP, mCP, mCBP, TPBi, TCTA, mTDAPB, ADN, DPEPO, m-MTDATA, Bphen, Alq, NPB, Spiro-TTB, Spiro-TPD, CzSi, DSBI, DBTDAS, Carbazole, Pyrene, Anthracene, Perylene, Coronene, Phenothroline, Quinoline, Acridine, Fluorene, TPSIL, T2T, TAPC, TAZ, and B3PYMPM.

[0057] This application also provides the application of the above-described composite material in ink preparation.

[0058] In one embodiment, the ink comprises a composite material and a solvent, the solvent comprising 1-methylnaphthalene:cyclohexylbenzene.

[0059] This application also provides a light-emitting device, see embodiments thereof. Figure 1The light-emitting device includes a first electrode 10, a light-emitting layer 20, and a second electrode 30 stacked together; wherein the material of the light-emitting layer includes the boron nitride compound described in the above embodiments, or the material of the light-emitting layer includes the composite material described in the above embodiments.

[0060] In one embodiment, the light-emitting device further includes a first carrier functional layer 40 and / or a second carrier functional layer 50;

[0061] The first charge carrier functional layer is located between the first electrode and the light-emitting layer, and the second charge carrier functional layer is located between the second electrode and the light-emitting layer.

[0062] In one embodiment, the first electrode is the anode and the second electrode is the cathode.

[0063] The materials of the anode and / or the cathode are independently selected from at least one of metallic materials, carbon materials, and metal oxides. The metallic materials include one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Yb, and Mg. The carbon materials include one or more of graphite, carbon nanotubes, graphene, and carbon fibers. The metal oxides include doped or undoped metal oxides. The doped metal oxides include one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO. Alternatively, they may include composite electrodes with metal sandwiched between doped or undoped transparent metal oxides. The composite electrodes include one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2.

[0064] In one embodiment, the first carrier functional layer includes a hole transport layer 41 and / or a hole injection layer 42, wherein the hole injection layer is disposed closer to the first electrode.

[0065] The hole transport layer is made of at least one of organic hole transport materials and inorganic hole transport materials. The organic hole transport materials include poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), poly(9-vinylcarbazole) (PVK), 9,9'-(1,3-phenyl)bis-9H-carbazole (mCP), 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), and N,N'-di(naphthyl-2-yl)-N,N' -Di(phenyl)biphenyl-4,4'-diamine (B-NPB), N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine (Spiro-NPB), N2,N7-DI-1-naphthyl-N2,N7,9,9-tetraphenyl-9H-fluorene-2,7-diamine (DPFL-NPB), 9,9-di(2-ethylhexyl)-N,N'-di-1-naphthyl-N,N'-diphenyl-9H-fluorene-2,7-diamine (DOFL-NPB), N4,N4'-di(4-vinylphenyl)-N4,N4'-di-1-naphthylbiphenyl-4,4'-diamine (VNPB), 3,6- Bis(9-phenyl-9H-carbazol-3-yl)-9-phenyl-9H-carbazole (Tris-PCz), 9,1-dihydro-9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-pyridine (PCzAc), N-biphenyl-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2-amine (PCbz-PA1), 9,9-dimethyl-N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9H-fluorene-2,7-diamine (DMFL-TPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (T PD), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine (Spiro-TPD), N,N,N',N'-tetra(2-naphthyl)-1,1'-biphenyl-4,4'-diamine (β-TNB), 2,2',7,7'-tetra(diphenylamino)-9,9'-spirobifluorene (Spiro-TAD), N,N'-bis(9,9-dimethyl-9H-fluorene-2-yl)-N,N'-diphenylbenzidine (BF-DPB), N,N,N',N'-tetraphenylbenzidinediamine (BPBPA), 4,4'-(diphenylmethylene)bis(N,N-diphenylaniline) (TCBPA), 9,9-Di[4-[di(bis(biphenyl-4-yl)amino]phenyl]fluorene (BPAPF), tri(4-biphenyl)amine (TBA), 4,4'-(diphenylsilanediyl)bis(N,N-diphenylaniline) (TSBPA), 4,4'-(9H-fluorene-9-alkylene)bis[N,N-bis(4-methylphenyl)-benzylamine (DTAF), polyvinylcarbazole, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzylamine Poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4”-tris(carbazole-9-yl)triphenylamine, 4,4'-di(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, doped graphene, undoped graphene, and C, 60 The inorganic hole transport material includes at least one of the following: doped or undoped NiO, WO3, MoO3, and CuO.

[0066] The hole injection layer is selected from at least one of high-conductivity organic molecular materials, transition metal oxides, and transition metal sulfur compounds; the high-conductivity organic molecular material is selected from poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, copper polyester carbonate, free phthalocyanine (H2PC), copper phthalocyanine (CuPc), platinum phthalocyanine (PtPC), and titanium dioxide. Phthalocyanine (TiOPC), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HAT-CN), 7,7,8,8-tetracyano-p-benzodiquinone dimethyl ether (TCNQ), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-di-1-naphthyl-biphenyl-4,4'-diamine (NPB-DPA), N,N'-diphenyl-N,N'-bis(4'-(N,N-di(1-naphthyl)-amino)-4-biphenyl)-benzidine (Di-NPB), N,N′-di(phenyl)-N,N 4′-bis(4′-(N,N-bis(phenylamino)-4-biphenyl)benzidine (TPT1), N,N'-diphenyl-N,N'-bis-[4-(N,N-di-p-tolylamino)phenyl]benzidine (NTNPB), N4,N4,N4',N4'-tetra(4-methoxyphenyl)-[1,1'-biphenyl]-4,4'-diamine (MeO-TPD), 4,4',4”-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 4,4'4"-tris(N,N-diphenylamino)triphenylamine (NATA) The transition metal oxide is selected from at least one of N2,N2'-(9,9-dimethyl-9H-fluorene-2,7-diyl)bis(9,9-dimethyl-N2,N7,N7-triphenyl-9H-fluorene-2,7-diamine)(3DMFL-BPA) and 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ); the transition metal oxide is selected from at least one of NiO, MoO3, WO3, CuO, and Cu2O; the transition metal sulfur compound is selected from at least one of MoS2, MoSe2, WS3, WSe3, and CuS.

[0067] In one embodiment, the second carrier functional layer includes an electron transport layer 51 and / or an electron injection layer 52, the electron injection layer being disposed closer to the second electrode.

[0068] The material of the electron transport layer 51 is selected from inorganic or organic materials; the inorganic material is selected from one or more of the following: doped or undoped zinc oxide, barium oxide, aluminum oxide, nickel oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, lithium titanium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc tin sulfide, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide, and barium titanate; the doped elements include one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium, and gadolinium; the organic material is selected from one or more of the following: quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, and hydroxyquinoline compounds.

[0069] The material of the electron injection layer 52 includes at least one of LiF, NaF, KF, CsF, RbF, LiF / Yb, CsN3, NaF / Yb, CsF / Yb, MgP, MgF2, Al2O3, Ga2O3, Cs2CO3, Rb2CO3, RbBr, and lithium tetrakis(8-hydroxyquinoline)boron (LiBq4).

[0070] This application also provides a display device comprising the boron nitride compound described in the above embodiments, or the composite material described in the above embodiments, or the light-emitting device described in the above embodiments.

[0071] The following specific embodiments will be used to illustrate the contents of this application in more detail and to further elaborate on this application, but these embodiments are by no means intended to limit this application.

[0072] Compound Examples 1-9

[0073] In this embodiment, the boron-nitrogen compound is prepared as follows:

[0074] (1) Preparation of compound III-1

[0075]

[0076] Compound II-1 is provided: 4',5'-bis(4-bromophenyl)spiro[fluorene-9,2'-imidazole] (DOI: 10.1002 / adma.202305310).

[0077] Add 4',5'-bis(4-bromophenyl)spiro[fluorene-9,2'-imidazole] (1 mmol, 528 mg) to a 25 mL Shrek reaction tube, along with palladium acetate (0.1 mmol, 22 mg), 2-(di-tert-butylphosphine)-3,6-dimethoxy-2'-4'-6'tri-1-propyl-1,1'-bisphenyl (0.25 mmol, 121 mg), cesium carbonate (4 mmol, 1304 mg), and boric acid (3 mmol, 186 mg). Then add 10 mL of NMP, purge with nitrogen, and evacuate under vacuum for 20 min. Stir the reaction mixture. The mixture was stirred and heated to 85°C for 24 hours. The reaction was then stopped and cooled to room temperature. A 2 mol / mL aqueous solution of hydrogen chloride was added to quench the reaction. The reaction solution was then extracted and washed repeatedly 3-4 times with dichloromethane (800 mL) and water (250 mL). The resulting organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was PE / DCM / EA = 10:3:2. Compound III-1 was obtained as a white solid with a yield of 80% and a melting point of 131.2°C–132.2°C. The mass spectrometry result was m / z = 403.44 [M+H]. + .

[0078] (2) Compounds III-2, III-3, III-4, III-5, and III-6 were synthesized using the same method as compound III-1, except that 4',5'-bis(4-bromophenyl)spiro[fluorene-9,2'-imidazole] was replaced with starting material 1, as shown in Table 1:

[0079]

[0080]

[0081] (3) Preparation of compound IV-1 using compound III-1 as a raw material

[0082]

[0083] Compound III-1 (1 mmol, 402 mg), 1-bromo-2,6-difluorobenzene (CAS: 64248-56-2) (2.5 mmol, 748 mg), and cesium carbonate (3 mmol, 975 mg) were added to a 50 mL two-necked flask. Then, 25 mL of DMF was added, and nitrogen gas was introduced. The mixture was evacuated using a vacuum pump for 20 min. The reaction solution was stirred and heated to 150 °C for 24 h. The reaction was then stopped and cooled to room temperature. The reaction solution was extracted, and the mixture was washed repeatedly 3 to 4 times with dichloromethane (800 mL) and water (250 mL). The resulting organic phase was dried with anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was PE / DCM / EA = 10:3:2. Compound IV-1 was obtained as a white solid, weighing 600 mg, with a yield of 80%. The mass spectrometry result was m / z = 749.31 [M+H]. + .

[0084] (4) The method for synthesizing compound IV-1 is used to synthesize compounds IV-2, IV-3, IV-4, IV-5, IV-6, and IV-7, except that compound III-1 is replaced with raw material 1. See Table 2 for details:

[0085] Table 2

[0086]

[0087]

[0088] (5) Preparation of compound V-1 using compound IV-1 as a raw material

[0089]

[0090] Compound IV-1 (1 mmol, 748 mg), 9H-carbazole (CAS: 86-74-8) (2.5 mmol, 417 mg), and cesium carbonate (3 mmol, 975 mg) were added to a 100 mL two-necked flask. Then, 50 mL of DMF was added, and nitrogen gas was introduced. The mixture was evacuated using a vacuum pump for 20 min. The reaction solution was stirred and heated to 150 °C for 24 h. The reaction was then stopped and cooled to room temperature. The reaction solution was extracted, and the mixture was washed repeatedly 3 to 4 times with dichloromethane (800 mL) and water (250 mL). The resulting organic phase was dried with anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was PE / DCM / EA = 10:3:2. Compound M1 was obtained with a yield of 80%, and the mass spectrometry result was m / z = 1043.51 [M+H]. + .

[0091] (6) Synthesize V-2, V-3, V-4, V-5, V-6, V-7, V-8, V-9, and V-10 using the same method as V1, except that IV-1 is replaced with raw material 1 and 9H-carbazole is replaced with raw material 2. See Table 3 for details.

[0092] Table 3

[0093]

[0094]

[0095]

[0096]

[0097] (7) Prepare compound M1 from compound V-1 as a raw material

[0098]

[0099] Compound IV-1 (1.6 mmol, 1197 mg) was added to a 100 mL two-necked flask, followed by 50 mL of ultra-dry trimethylbenzene. Nitrogen gas was introduced, and the flask was evacuated at -30 °C for 20 min using a vacuum pump. Then, tert-butyllithium (2.5 mL, 3.2 mmol, 1.3 M dichloromethane solution) was slowly added dropwise using a syringe. The temperature was then slowly raised to room temperature, followed by heating to 90 °C and stirring for 3 h. The reaction apparatus was then cooled to -30 °C, and boron tribromide (3.2 mL, 3.2 mmol, 1.0 M dichloromethane solution) was added using a syringe. The temperature was then raised to 90 °C. The reaction was carried out at room temperature for 3 hours, then cooled to 0°C and diisopropylethylamine (2 ml) was added. The reaction solution was then stirred and heated to 170°C for 24 hours. The reaction was stopped, cooled to room temperature, and sodium acetate was added to quench the reaction. The reaction solution was extracted and washed repeatedly 3 to 4 times with dichloromethane (800 mL) and water (250 mL). The obtained organic phase was dried with anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography with eluent PE / DCM / EA = 10:3:2. Compound M1 was obtained in 80% yield, and the mass spectrometry result was m / z = 901.21 [M+H]. + .

[0100] The 1H NMR spectrum data of compound M1 are as follows:

[0101] 1H NMR(500MHz,Chloroform-d)δ8.22-8.13(m,4H),8.07(d,J=2.1Hz,2H),7.82(dd,J=7.9,1.4Hz,2H),7.77(dd,J=7.9,1.3Hz,2H), 7.67-7.51(m,12H),7.48-7.40(m,3H),7.38-7.33(m,2H),7.32-7.26(m,3H),7.23(d,J=8.4Hz,2H),6.88(dd,J=7.9,1.1Hz,2H).

[0102] (8) Synthesize M4, M12, M16, M21, M26, M32, M37, M38, and M42 using the same method as for synthesizing M1, except that V-1 is replaced with raw material 1. See Table 4 for details.

[0103] Table 4

[0104]

[0105]

[0106]

[0107] Device Example 1

[0108] This embodiment provides an organic light-emitting device with the following stacked structure: ITO / 4P-NPD:F4TCNQ(30nm) / 4P-NPD(25nm) / EML(35nm) / LIQ:ET1(25nm) / Yb(1nm) / Al(100nm).

[0109] The method for fabricating the organic light-emitting device is as follows:

[0110] Step 1: Pretreatment of Indium Zinc Oxide (ITO) Coated Glass (Specifications: Thickness 45nm, Thin Film Resistance 10Ωm-2, Surface Size 30mm×30mm): The glass substrate is sequentially cleaned using a cleaning machine, with each cleaning cycle lasting 120 seconds, to thoroughly remove stains and dust from the surface. It is then baked on a 230℃ hot plate for 30 minutes. Afterward, it is dried in an electric hot air drying oven for 24 hours. Subsequently, the dried glass substrate is subjected to UV exposure and O2 plasma treatment for 15 minutes to reduce surface enthalpy.

[0111] Step 2: Using the pretreated ITO glass substrate as the device anode, the 4P-NPD is then placed in a nitrogen glove box.

[0112] F4TCNQ (9:1) as HI was dissolved in cyclohexanone (concentration 30 mg / ml) and filled into an inkjet printer cartridge. 15 picoliters of HI layer ink were injected into each pixel, and the ink was subjected to vacuum distillation (VD) for 5 minutes (vacuum degree 1 × 10⁻⁴ mPa) to form a 30 nm thick HI layer. The ink was then annealed at 230°C for 30 minutes. The structural formulas of 4P-NPD and F4TCNQ are as follows:

[0113]

[0114] Step 3: Then, 4P-NPD dissolved in a mixed solution of xylene and cyclohexylbenzene is used as a hole transport layer material (concentration of 20 mg / ml). After filtration, it is poured into the inkjet printer cartridge. 12 picoliters of HT layer ink are injected into each pixel light-emitting point and VD is performed for 5 minutes (vacuum degree of 1×10-4 mPa) to form a 25 nm thick HT layer. Annealing is then performed at 230℃ for 30 minutes.

[0115] Step 4: The dissolved luminescent layer material (concentration 20 mg / ml, solvent: 1-methylnaphthalene:cyclohexylbenzene = 2:8) is then formulated into ink and filled into the inkjet printer cartridge. 10 picoliters are then printed onto each pixel of the aforementioned HT layer and subjected to vacuum drying (VD) for 5 minutes (vacuum degree 1 × 10⁻⁴ mPa) to form the EML layer. This layer is then annealed at 140°C for 20 minutes, resulting in a thickness of 35 nm. The luminescent layer material comprises BH-1 (95 wt%) and compound M1 (5 wt%), with BH-1 as the host material and M1 as the guest material.

[0116] The structural formula of BH-1 is as follows:

[0117]

[0118] Step 5: Then transfer it to a vacuum evaporation chamber (vacuum degree 5×10-7 Pa) for vacuum evaporation of LiQ:ET1 (rate ratio 7:3) to obtain ET with a thickness of 25 nm; wherein, the structural formula of ET1 is:

[0119]

[0120] Step 6: Then, deposit a 1 nm thick layer of Yb as EI on the above ET;

[0121] Step 7: Evaporate a 100nm thick layer of Al above EI to serve as the cathode for the OLED device. Finally, encapsulate it by UV curing and bake it for 20 minutes to prepare a complete organic electroluminescent device.

[0122] Organic electroluminescent device Example 2

[0123] The only difference from the organic electroluminescent device of Example 1 is that compound M1 is replaced with compound M4.

[0124] Organic electroluminescent device Example 3

[0125] The only difference from the organic electroluminescent device of Example 1 is that compound M1 is replaced with compound M12.

[0126] Organic electroluminescent device Example 4

[0127] The only difference from the organic electroluminescent device of Example 1 is that compound M1 is replaced with compound M16.

[0128] Organic electroluminescent device Example 5

[0129] The only difference from Example 1 of the organic electroluminescent device is that the host material BH-1 is replaced with BH-2, and compound M1 is replaced with compound M21. The structural formula of BH-2 is as follows:

[0130]

[0131] Organic electroluminescent device Example 6

[0132] The only difference from the organic electroluminescent device of Example 5 is that compound M21 is replaced with compound M26.

[0133] Organic electroluminescent device Example 7

[0134] The only difference from the organic electroluminescent device of Example 1 is that compound M1 is replaced with compound M32.

[0135] Organic electroluminescent device Example 8

[0136] The only difference from the organic electroluminescent device of Example 1 is that compound M1 is replaced with compound M37.

[0137] Organic electroluminescent device Example 9

[0138] The only difference from the organic electroluminescent device of Example 5 is that compound M21 is replaced with compound M38.

[0139] Organic electroluminescent device Example 10

[0140] The only difference from the organic electroluminescent device of Example 5 is that compound M21 is replaced with compound M42.

[0141] Organic electroluminescent devices Comparative Example 1

[0142] The only difference from Example 5 of the organic electroluminescent device is that compound M21 is replaced with compound BD01. The structural formula of BD01 is as follows:

[0143]

[0144] Organic electroluminescent devices Comparative Example 2

[0145] The only difference from Example 1 of the organic electroluminescent device is that compound M1 is replaced by compound BDO2. The structural formula of BDO2 is as follows:

[0146]

[0147] Organic electroluminescent devices comparative example 3

[0148] The only difference from Example 5 of the organic electroluminescent device is that compound M21 is replaced with compound BDO3. The structural formula of BDO3 is as follows:

[0149]

[0150] Organic electroluminescent devices comparative example 4

[0151] The only difference from Example 5 of the organic electroluminescent device is that compound M21 is replaced with compound BD04. The structural formula of BD04 is as follows:

[0152]

[0153] Organic electroluminescent devices comparative example 5

[0154] The only difference from Example 1 of the organic electroluminescent device is that compound M1 is replaced by compound BD05. The structural formula of BD05 is as follows:

[0155]

[0156] Organic electroluminescent devices comparative example 6

[0157] The only difference from Example 5 of the organic electroluminescent device is that compound M21 is replaced with compound BD06. The structural formula of BD06 is as follows:

[0158]

[0159] The photoelectric performance of the organic electroluminescent devices described in Examples 1-10 and Comparative Examples 1-6 was tested. Specifically, the maximum current efficiency (CEmax) was tested using an IV-L testing system, and the T95 lifetime (T95@1000nit) at a luminous intensity of 1000nit was tested using a lifetime testing system. The relevant test data are shown in Table 5 below.

[0160] Table 5

[0161]

[0162]

[0163] As shown in Table 1, incorporating the boron-nitrogen compound of this application as a guest into the light-emitting layer can significantly narrow the full width at half maximum (FWHM) of OLED devices and improve EQE and stability compared to existing guest materials.

[0164] Obviously, the embodiments described above are only some embodiments of this application, not all embodiments. The accompanying drawings show preferred embodiments of this application, but do not limit the patent scope of this application. This application can be implemented in many different forms; rather, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing specific embodiments, or make equivalent substitutions for some of the technical features. Any equivalent structures made using the content of this application's specification and drawings, directly or indirectly applied to other related technical fields, are similarly within the scope of patent protection of this application.

Claims

1. A boron-nitrogen compound, characterized in that, Its general structural formula is shown in equation (I): Each time X appears, it is independently selected from either carbon or nitrogen; A includes sulfonyl groups, C6-C6 groups. 60 At least one of the azirroyl groups; R1 to R4 are each independently selected from hydrogen, deuterium, amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, and substituted or unsubstituted C1 to C4 groups. 30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkyl mercapto, substituted or unsubstituted C1-C 30 Alkylamine, substituted or unsubstituted C1-C 30 Alkyl carbonyl, substituted or unsubstituted C1-C 30 One or more of the following: alkoxycarbonyl, aryl with 6 to 60 substituted or unsubstituted ring atoms, heteroaryl with 5 to 60 substituted or unsubstituted ring atoms, arylamino with 6 to 60 substituted or unsubstituted ring atoms, aryloxy with 6 to 60 substituted or unsubstituted ring atoms, arylthiol with 6 to 60 substituted or unsubstituted ring atoms, heteroarylamino with 5 to 60 substituted or unsubstituted ring atoms, heteroaryloxy with 6 to 60 substituted or unsubstituted ring atoms, and heteroarylthiol with 6 to 60 substituted or unsubstituted ring atoms; When substituted, each substituent is independently selected from hydrogen, deuterium, halogen, amino, hydroxyl, carboxyl, nitro, sulfonic acid, mercapto, cyano, C1-C2. 30 One or more combinations of alkyl, aryl with 6 to 30 ring atoms, and heteroaryl with 5 to 30 ring atoms.

2. The boron-nitrogen compound according to claim 1, characterized in that, R1 to R4 are each independently selected from one of the following: hydrogen, deuterium, halogen atom, cyano group, C1 to C5 alkyl group, C1 to C5 alkoxy group, C1 to C5 alkyl mercapto group, and C1 to C5 alkyl amine group.

3. The boron-nitrogen compound according to claim 1 or 2, characterized in that, A is selected from one or more of the following structural formulas: Each time Y appears, it is independently selected from carbon or nitrogen, and at least one Y in each structure is selected from nitrogen; n1 to n5 are integers from 1 to 8; Each of R5 to R9 is independently selected from one or more combinations of hydrogen, deuterium, halogen atom, cyano, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkyl mercapto, C1-C5 alkylamino, substituted or unsubstituted aryl group having 6 to 10 ring atoms; when substituted, each of the substituents is independently selected from one or more combinations of hydrogen, deuterium, halogen, amino, hydroxyl, carboxyl, nitro, sulfonic acid group, mercapto, cyano, C1-C5 alkyl, aryl group having 6 to 10 ring atoms, heteroaryl group having 5 to 10 ring atoms.

4. The boron-nitrogen compound according to claim 3, characterized in that, The A is selected from one of the structures shown in equations (1-1) to (1-24): In equations (1-1) to (1-24), * represents the connection site.

5. The boron-nitrogen compound according to claim 4, characterized in that, The boron nitride compound is selected from at least one of the structures shown in M1 to M42:

6. A composite material, characterized in that, Includes organic functional materials and boron-nitrogen compounds as described in any one of claims 1 to 3.

7. The composite material according to claim 6, characterized in that, The mass ratio of the organic functional material to the boron-nitrogen compound ranges from (80:20) to (99:1), preferably from (95:5) to (99:1); and / or, The organic functional materials include at least one of BH1, BH2, CBP, mCP, mCBP, TPBi, TCTA, mTDAPB, ADN, DPEPO, m-MTDATA, Bphen, Alq, NPB, Spiro-TTB, Spiro-TPD, CzSi, DSBI, DBTDAS, Carbazole, Pyrene, Anthracene, Perylene, Coronene, Phenothroline, Quinoline, Acridine, Fluorene, TPSIL, T2T, TAPC, TAZ, and B3PYMPM.

8. A light-emitting device, characterized in that, It includes a first electrode, a light-emitting layer, and a second electrode stacked together; The material of the light-emitting layer includes the boron nitrogen compound according to any one of claims 1 to 5, or the material of the light-emitting layer includes the composite material according to claim 6 or 7.

9. The light-emitting device according to claim 8, characterized in that, The light-emitting device further includes a first carrier functional layer and / or a second carrier functional layer; The first charge carrier functional layer is located between the first electrode and the light-emitting layer, and the second charge carrier functional layer is located between the second electrode and the light-emitting layer.

10. The light-emitting device according to claim 9, characterized in that, The first electrode is the anode, and the second electrode is the cathode. The materials of the anode and / or the cathode are independently selected from at least one of metallic materials, carbon materials, and metal oxides. The metallic materials include one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Yb, and Mg. The carbon materials include one or more of graphite, carbon nanotubes, graphene, and carbon fibers. The metal oxides include doped or undoped metal oxides, and the doped metal oxides include ITO, FTO, ATO, AZO, and G. One or more of ZO, IZO, MZO, and AMO, or a composite electrode comprising a metal sandwiched between doped or undoped transparent metal oxides, wherein the composite electrode comprises one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2; and / or, The first carrier functional layer includes a hole transport layer and / or a hole injection layer, wherein the hole injection layer is disposed closer to the first electrode; the material of the hole transport layer includes at least one of organic hole transport materials and inorganic hole transport materials, wherein the organic hole transport material includes poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), poly(9-vinylcarbazole) (PVK), 9,9'-(1,3-phenyl)bis-9H-carbazole (mCP), 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'- Biphenyl-4,4'-diamine (NPB), N,N'-di(naphthyl-2-yl)-N,N'-di(phenyl)biphenyl-4,4'-diamine (B-NPB), N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirobis[9H-fluorene]-2,7-diamine (Spiro-NPB), N2,N7-DI-1-naphthyl-N2,N7,9,9-tetraphenyl-9H-fluorene-2,7-diamine (DPFL-NPB), 9,9-di(2-ethylhexyl)-N,N'-di-1-naphthyl-N,N'-diphenyl-9H-fluorene-2,7-diamine (DOFL-NPB), N4,N4'-di(4-vinylphenyl)-N4,N4'-di-1-naphthyl Bisphenyl-4,4'-diamine (VNPB), 3,6-bis(9-phenyl-9H-carbazol-3-yl)-9-phenyl-9H-carbazole (Tris-PCz), 9,1-dihydro-9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-pyridine (PCzAc), N-biphenyl-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2-amine (PCbz-PA1), 9,9-dimethyl-N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9H-fluorene-2,7-diamine (DMFL-TPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine (VNPB), 3,6-bis(9-phenyl-9H-carbazol-3-yl)-9-phenyl-9H-fluorene-2,7-diamine (DMFL-TPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-diphenyl-4,9'-dimethyl-9H-fluorene-2,7-diamine (DMFL-TPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-diphenyl-4,9'-diphenyl-9H-carbazol-3-yl)-diphenyl-9H-fluorene-2,7-diamine (DMFL-TPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-diphenyl-9H ... Benzene-4,4'-diamine (TPD), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine (Spiro-TPD), N,N,N',N'-tetra(2-naphthyl)-1,1'-biphenyl-4,4'-diamine (β-TNB), 2,2',7,7'-tetra(diphenylamino)-9,9'-spirobifluorene (Spiro-TAD), N,N'-bis(9,9-dimethyl-9H-fluorene-2-yl)-N,N'-diphenylbenzidine (BF-DPB), N,N,N',N'-tetraphenylbenzidinediamine (BPBPA), 4,4'-(diphenylmethylene)bis(N,N-diphenylaniline) (TCBPA), 9,9-Di[4-[di(bis(biphenyl-4-yl)amino]phenyl]fluorene (BPAPF), tri(4-biphenyl)amine (TBA), 4,4'-(diphenylsilanediyl)bis(N,N-diphenylaniline) (TSBPA), 4,4'-(9H-fluorene-9-alkylene)bis[N,N-bis(4-methylphenyl)-benzylamine (DTAF), polyvinylcarbazole, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzylamine Poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4”-tris(carbazole-9-yl)triphenylamine, 4,4'-di(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, doped graphene, undoped graphene, and C, 60 The inorganic hole transport material comprises at least one of the following: doped or undoped NiO, WO3, MoO3, and CuO; the hole injection layer is selected from at least one of high-conductivity organic molecular materials, transition metal oxides, and transition metal sulfide compounds; the high-conductivity organic molecular material is selected from poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, and polyester. Copper carbonate, free phthalocyanine (H2PC), copper phthalocyanine (CuPc), platinum phthalocyanine (PtPC), titanium phthalocyanine (TiOPC), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HAT-CN), 7,7,8,8-tetracyano-p-benzodiquinone dimethyl ether (TCNQ), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-di-1-naphthyl-biphenyl-4,4'-diamine (NPB-DPA), N,N'-diphenyl-N,N'-di(4'-(N,N-di(1-naphthyl)-amino)-4-biphenyl)-benzidine (Di-NPB), N,N′-di(phenyl)-N,N′-di(4′-(N,N-di(phenylamino)-4-biphenyl)benzidine (TPT1), N,N'-diphenyl-N,N'-di-[4-(N,N-di-p-tolylamino)phenyl]benzidine (NTNPB), N4,N4,N4',N4'-tetra(4-methoxyphenyl)-[1,1'-biphenyl]-4,4'-diamine (MeO-TPD), 4,4',4”-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 4,4'4"-tris(N,N-diphenylamino) At least one of triphenylamine (NATA), N2,N2'-(9,9-dimethyl-9H-fluorene-2,7-diyl)bis(9,9-dimethyl-N2,N7,N7-triphenyl-9H-fluorene-2,7-diamine) (3DMFL-BPA), and 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ); the transition metal oxide is selected from at least one of NiO, MoO3, WO3, CuO, and Cu2O; the transition metal sulfide is selected from at least one of MoS2, MoSe2, WS3, WSe3, and CuS; and / or, The second carrier functional layer includes an electron transport layer and / or an electron injection layer, wherein the electron injection layer is disposed closer to the second electrode; the material of the electron transport layer is selected from inorganic or organic materials; the inorganic material is selected from one or more of the following: doped or undoped zinc oxide, barium oxide, aluminum oxide, nickel oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, lithium titanium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc tin sulfide, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide, and barium titanate; the doped element... The elements include one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium, and gadolinium; the organic material is selected from one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, and hydroxyquinoline compounds; the material of the electron injection layer includes at least one of LiF, NaF, KF, CsF, RbF, LiF / Yb, CsN3, NaF / Yb, CsF / Yb, MgP, MgF2, Al2O3, Ga2O3, Cs2CO3, Rb2CO3, RbBr, and lithium tetrakis(8-hydroxyquinoline)boron (LiBq4).

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